Azo dyes



United States Patent 3,117,956 A20 DYES Guenter Lange, Ludwigshafen (Rhiae)-Gartenstadt, and Hans Guenter W ippei, Ludwigshafen (Rhine), Germany, assignors to Baziische Aniiin- & Soda-'Fabrik Aktiengesellschait, Ludwigshaien (Rhine), Germany No Drawing. Filed Feb. 15, 1961, Ser. No. 89,359 Claims priority, application Germany Feb. 18, 1960 Claims. (Cl. 269-152) This invention relates to new water-insoluble azo dyes which contain in the molecule a radical of the general formula:

to a process for their production and to their use for dyeing textile materials and shaped articles of synthetic materials. In the said Formula I, R stands for an alkyl radical which may be substituted by non-ionic radicals and R for an alkylene group which may bear further non-ionic radicals. R and R may be connected to each other either directly or by way of hetero atoms, and one of the radicals R and R may be connected to a benzene ring at the ortho position to the amino group.

The term textile materials includes fibers, flock, threads and Woven and non-woven fabrics. The term shaped articles includes films and sheets. The term synthetic materials includes linear polyamides, such as nylon 6, nylon 66 or nylon 11, and linear polyurethanes. The dyes of this invention are especially suitable for dyeing or printing cellulose 2 /z-acetate, cellulose triacetate and polyethylene terephthalate.

It is an object of this invention to provide dyes which will dye especially textile materials of the three last-mentioned substances bright shades of excellent fastness to rubbing and light.

Another object of this invention is to provide dyes which dye textile materials of cellulose 2 /2-acetate with outstanding waste gas fastness.

The new dyes of this invention are obtained by coupling aromatic or heterocyclic diazo compounds which may contain non-ionic radicals with compounds of the benzene series which contain attached to a benzene ring a substituted amino group of the above general Formula I which couples at the para position to this amino group and may bear further non-ionic radicals in the benzene ring, or by reacting azo dyes of the general formula:

A-N N-B II in which A denotes the radical of a diazotizable aromatic amine or heterocyclic amine and B denotes a radical of the benzene series which bears at the paraposition to the azo group a substituted amino group of the general formula:

in which R and R have the meanings given above with 2,3-dichlortetrahydrofurane.

Diazotizable amines suitable for the production of the new dyes include aminobenzene and its derivatives containing non-ionic radicals, such as halogen atoms, nitro, cyano, alkyl, acylamino, alkylsulfonyl, trifuoromethyl, alkoxy and/or carbalkoxy groups; also Z-aminothiazole and 2-amino-l,3,4-thiadiazole as well as their derivatives substituted by the said non-ionic groups or by alkyl or aryl radicals.

Suitable coupling components which contain the radical of the above general Formula I include the 3-chloro- H 3,li7,5 Patented Jan. 14, ieea 2 tetrahydrofuryl-(2)-hydroxy derivatives of N,N-dialkylaminobenzenes, such as N-ethyl-N- 3-chlorotetrahydrofuryl- (2) -hydroxyethyl) aminobenzene,

-N-cyanoethyl-N-( 3-chlorotetrahydrofuryl- 2) -hydroxyethyl)-amino benzene,

N-chloroethyl-N- 3 -chlorotetrahydrofuryl- (2) -hydroxyethyl) -aminobenzene,

N- 2- 3-chlorotetrahydrofuryl- (2) -hydroxy) -3-chloropropyl]-N-ethylaminobenzene,

N,N-bis-( 3-chlorotetrahydro-furyl- (2) -hydroxyethyl) aminobenzene,

N- [2- 3 -chlorotetrahydrofuryl- (2) -hydroxy) -3 -cyanopropyl] -N-ethylaminobenzene,

N- 3 -chlorotetrahydrofuryl- (2) -hydroxyethy1) -N- (2- acetoxyethyl) -aminob enzene,

N- 3-chlorotetrahydrofuryl-( 2) -hydroxyethy1) -N-2- meth oxyethyl -aminob enzene,

N 3 -chlorotetrahydrofuryl- 2) -hydroxyethyl) -N- propylaminobenzene,

N- 3 -chlorotetrahydrofuryl- 2) -hydroxyethyl) -N- (2,2-

difluoroethyl) -aminob enzene and the m-alkyl, m-alkoxy, m-trifluoromethyl, m-acylamino, m-cyano and m-halogen derivatives of these compounds.

Other useful coupling components include N-alkyl-3-chlorotetrahydrofuryl- (2) -hydroxy-tetrahydroquinolines, such as N-butyl-3 [3-chlorotetrahydrofuryl-(2) -hydroxy] -7- methyl-1,2,3,4 tetrahydroquinoline, and

N -alkyl- [3 -chlorotetrahydrofuryl- (2) -hydroXy] -phenomorpholines, such as N-ethyl-3 [3 -chlorotetrahydrofury1- 2) -hydroxy] phenomorpholine.

These coupling components are obtained by reaction of appropriate compounds of the benzene series, capable of coupling which bear the group of the Formula III above, with 2,3-dichlorotetrahydrofurane.

The reaction of the said compounds capable of coupling with 2,3-dichlorotet1'ahydrofurane may be effected by slowly introducing an about equimolar amount of 2,3-dichlorotetrahydrofurane into the coupling component at temperatures between 0 and C., preferably at room temperature. An inert solvent, for example dioxane, maybe coemployed. In some cases, it is advisable to heat the reaction mixture for a short time (about 10 minutes) at 50 to C., especially 100 C., to complete the reaction. The reaction is complete when a sample taken from the reaction mixture is uniform in a paper chromatogram after having been sprayed with an aqueous solution of nitrosamine. The coupling components obtained may be used for the production of the new azo dyes Without purification.

The production of 2,3-dichlorotetrahydrofurane is described for example in Liebigs Annalen der Chemie, vol. 596 (1955), p. 113.

Dyes of the general Formula II above are known; they can be synthesized from the above-mentioned diazo compounds and the above-mentioned compounds capable of coupling and containing the group of the general Formula 111 above. The reaction of these dyes with 2,3- dichlorotetrahydrofurane is carried out in the same way as above described for the production of the coupling components.

Of the new dyes of this invention, those are especially preferred in which R in the above formulae stands for a radical of the formula:

in which R has the meaning given above, and those which have the general formula:

in which D denotes one of the radicals:

R HC-N N-N R a low molecular weight alkyl, hydroxyalkyl or cyanoalkyl radical or the radical:

R a low molecular weight al-kylene, halogenalkylene or cyanalkylene radical, R, a hydrogen atom or a low molecular weight alkoxy radical, R; a hydrogen or halogen atom or a low molecular weight alkyl, trifiuoromethyl or acylamino radical, R a hydrogen or halogen atom, a cyano, triiiuoromethyl, low molecular Weight alkoxy or alkyl sulfonyl radical, R a hydrogen atom or a nitro radical, and R 2. low molecular weight alkyl radical or a phenyl radical.

The following examples illustrate the production and use of the new dyes but do not limit the invention. The parts and percentages specified in the examples are by weight.

Example 1 A mixture of 13.8 parts of 1-amino-4-nitrohenzene, 40 parts of concentrated hydrochloric acid and 40 parts of water is stirred for two hours at room temperature, 200 parts of ice are added and a solution of 6.1 parts of sodium nitrite in 20 parts of Water is introduced at to C. The whole is stirred for 20 minutes, any excess of nitrite present removed by adding aminosulfonic acid and the diazo solution filtered. The filtrate is gradually added to a solution of 30.9 parts of the reaction product derived from N-(Z-cyanoethyl) N (Z-hydroxyethyD- aminobenzene and 2,3-dichlorotetrahydrofurane in a mixture of parts of water and 10 parts of concentrated hydrochloric acid. After 30 minutes, '35 parts of anhydrous sodium acetate are added to this mixture, the whole is stirred for an hour and the reaction product filtered olf. It is washed with Water and dried at about 40 C. under reduced pressure. A dye is obtained which dyes polyethylene glycol terephthalate bright red shades of good rubbing and light fastness.

Dyes with similar properties are obtained in the same Way by using the compounds listed in the following table as coupling components instead of the reaction product from N-(Z-cyanoethyl)-N-(2-hydroxyethyl) aminobenzene and 2,3-dichlorotetrahydrofurane.

Similar dyes of bluish shade are obtained by using 16.8 parts of 1-amino-2-methoxy-4-nitrobenzene or 17.3 parts of 1-arnino-2-chlor-4-nitrobenzene instead of lamino-4-nitrob enzene Shade of Example Drazo component Coupling component dyeing on No. cellulose acetate l 2 5 5 OzN-NH1 N Red.

otntoo1'- l O HiCN e--. OZNQNHZ N Red.

ezmoj 7 Cl l (32H; 7.... om-Q-Nm N Bede CH:?HCH2CN l O f Cl Shade of Example Dmzo component Coupling component dyeing on No. cellulose acetate OCH I /C2H5 s O2NNH2 Q-N Red.

O l czHio CH; 1

Cl 2: 5 9 O:N-NH2 N Scarlet. O

(hngoj 1 Cl I CZH4CN w O oimoj 1 C1 11 OEN NH? N\ Red.

CHQCHCHQCN l O f i 01 Example 13 A mixture of 5.15 parts of l-amino-4-nitro-6-trifiuoromethylbenzene, 25 parts of Water and 25 parts of concentrated hydrochloric acid is stirred for two hours at room temperature, 20 parts of ice are added and a solution of 1.5 parts of sodium nitrite in 5 parts of Water is added. Any excess of nitrite present is destroyed after two hours by adding aminosulfonic acid and the solution filtered. The filtrate is gradually introduced at 0 to 5 C. into a solution of 7 .4 parts of the reaction product of N-ethyl-N-(Z-hydroxyethyl)-aminobenzene with 2,3-dichlorotetrahydrofurane in 6 parts of Water. 1.3 parts of sodium acetate are added to the mixture, the whole is stirred for 12 hours and the deposited reaction product is tered ed. The resultant dye is Washed with water and dried at C. under reduced pressure. t dyes polyethylene glycol terephthalate powerful red shades of good fastness to rubbing.

Dyes of similar properties are obtained by using as coupling components the compounds listed in the following table instead of the reaction product from N-ethyl- N-(Z-hydroxyethyl)-aminobenzene and 2,3-dichlorotetrahydrofurane:

Shad f Example Coupling component dyeing 811 No. cellulose acetate /C2H CN 14 @N Red.

ozmoj 1 Cl CzHs 15 @N Red.

(DEPTH-CHEN O 0, 1 all CQH5 1s N\ 0 Ruby.

Example 17 Shade of 24- parts of 1-arnino-4-nitrobenzene-Z-methylsulfone are Example o p component dye n on o No. cellulose introduced while stirring at C. into a mixture of 35 acetate parts of nitrosylsulfuric acid with a content of 12.1% of dinitrogen trioxide and 25 parts of concentrated sulfuric 0,21 acid. After 12 hours, the diazo solution is poured onto 20 Ruby 200 parts of ice, filtered and the filtrate introduced into a solution of 29.6 parts of a reaction product derived from CHPOHWOHZCN N-ethyl-N-(2-hydroxyethyl)-arnino benzene and 2,3-di- 0 l 0 chlorotetrahydrofurane in 25 parts of water. After stir- 1 ring for four hours, the crystalline dye is filtered ofi, washed with water and dried at 40 C. under reduced pressure. It dyes cellulose acetate ruby red shades of very Example 21 good Washmg, gas and hght 18 parts of 2-amino-5-phenyl-1,3,4-thiadiazole are in- Instead of the above'mentloned coupling component troduced while stirring at 0 to 5 C. into a mixture of 35 t aminfis 0f the following table Yield y with Similar parts of nitrosylsulfuric acid with a content or" 13.1% of properties: dinitrogen trioxide, 25 parts of concentrated sulfuric acid and 109 parts of a mixture of anhydrous acetic acid and propionic acid at the ratio of 17:3. Another 100 parts of the acetic acid/propionic acid mixture are added at 0 to 5 C. to the mixture obtained and after three hours shade or 4 parts of urea are added. The solution is slowly intro- Example Coupling component dyetngon duced at 0 to 5 C. into a mixture of 30.9 parts of 513132 the reaction product derived from N-(2-cyanoethyl)-N- (Z-hydroxyethyl)-aminobenzene and 2,3-dichlorotetrahy- C2115 drofurane, 50 parts of Water and 10 parts of hydrochloric acid of the density 1.10, the mixture is stirred for an hour 18 k 0 Ruby and then poured onto 100 parts of ice. The dye obtained l CZH-LO is filtered oft", Washed with Water and dried at 50 C. CH3 7 under reduced pressure. It dyes synthetic linear poly- Clamides and polyesters bright red shades of excellent wet CZHlCN fastness. A similar dye with excellent Waste gas fastness is ob- 19 0 tained by using Z-amino-S-ethylthiadiazole instead of 2- CzH O- W amino-5-phenylthiadiazole.

Similar dyes can be prepared from the components of Cl the following table:

Shade of Example Diazo component Coupling component dyeing on No. cellulose acetate l 22 Q- S NH2 N\ Scarlet.

CzH -0 W ..l.

N-N 02H .3 @l la. N S

CHg(!3H-CH2CN f l Cl T 0.1139 24 l S o l CgHgO T l Cl Shade of Exa mple Diazo component Coupling component dy ifi 011 1'0. ce S9 acetate N N 2 s 25 Howl -NHz -N Red.

0 C2H40( l Cl-- CQHQCN 26 ma im N 0 021140 01L.

N 0 m 21 Hc NH, -N\ Red.

CHCHCHCN l o "i l L If? 2s H5ci Nin N\ 0 Do.

1 curl-0 H3 c1 canton 29 :CQ N Z N\ 0 ra g C2H4H OCH: T

' onnoN 3 s 2 2 N\ 0 DO- I 0,1Lo- 01 l ozmcN 3L; H5CZ\S NH3 Q 0 DO.

I 0 1140 C'Fa W 32 H5CZ \SJNHZ 'N\ CH2-(|3H-CH2C1 O f 1 Cl Example 33 100 parts of a mixture of anhydrous acetic acid and propionic acid at the ratio 17:3 are introduced at 0 to 5 C. into a mixture of 31.7 parts of nitrosylsulfuric acid with a dinitrogen trioxide content of 13.1% and parts of concentrated sulfuric acid, and then 14.5 parts of 2- amino-S-nitro-1,3-thiazole are added to the mixture at 0 to 5 C. Another 100 parts of the said acetic acid/ ropionic acid mixture are added and, after three hours, 8 parts of urea While stirring further at 0 to 5 C. The resultant clear solution is slowly introduced at 0 to 5 C. into a solution prepared as follows: 13.2 parts of l- (bis (Z-hydroxyethyl)-arnino)-2-methoxy-5-acetylaminobenzene are dissolved in 10 parts of dioxane and the reaction mixture, after adding 7.7 parts of 2,3-dichlorotetrahydrofurane, is heated for 15 minutes at to 98 C. 33 parts of Water are added at 35 C. to the resultant mixture and, after cooling to 0 C., 200 parts of ice.

After stirring for an hour, the reaction mixture is introduced into 3000 parts of ice Water, the deposited dye is filtered off and dried at 30 C. under reduced pressure. It dyes cellulose acetate greenish blue shades of excellent Waste gas fastness and excellent wet fastness.

Dyes with similar properties are obtained when the following coupling components are used instead of 1-(bis-(2 hydroxyethyl) -amino) -2-methoxy-S-acetylarninobenzene Shade of Example Coupling component dyeing on No. cellulose acetate CQHS l C'zHiOH 34 N Greenish blue. 021140 BN6 0 CH C2H4OH 3o N\ D0.

0 CQHiO- BIG 0 CH;

O GEES i C2H-1O 36 N Do.

l C2H4O HNC 0 CH3 2 40- 37 N Do.

C2Hi0- HN-C 0 CH3 CZHAO HN-C 0 CH I C2H CN 39 N Do.

O 02 40 HNO 0 CH3 Example 40 A mixture of 7.85 parts of 4-nitro-4'-[N-ethyl-N-(Z-hydroxyethyl)-amino]-azobenzene, 35 parts of dioxane, 5 parts of N-methylpyrrolidone and 7 parts of 2,3-dichlorotetrahydrofurane is heated for an hour at 100 C. The reaction mixture is then introduced into 100 parts of Water and the deposited precipitate filtered 01f and dried at 50 C. under reduced pressure. A dye is obtained which is identical with that obtainable according to Example 2.

The dye described in Example 9 can also be obtained by using 8.7 parts of 4-nitro-2-chlor-4'-[N-ethyl-N-(Z-hydroxyethyl)-arnino]-azobenzene instead of the above 4- nitro-4'- [N-ethyl-N- (Z-hydroxyethyl) -amjno] -azobenzene.

Example 41 13.3 parts of 1-amino-2,4-dinitrobenzene-6-methylsulfone are introduced at 0 to 5 C. While stirring into a mixture of 16 parts of nitrosylsulfuric acid with a content of 13.1% of dinitrogen trioxide and 22 parts of concentrated sulfuric acid. After stirring for three hours, the diazo solution is added at 0 to 5 C. to a solution which has been prepared as follows:

13.4 parts of 1-[bis-(2-hydroxyethyl)-amino]-2-methoxy-S-acetylaminobenzene are dissolved in 10 parts of 12 dioxane and the reaction mixture is heated for 15 minutes at to 98 C. after adding 7.2 parts of 2,3-dichlorotetrahydrofurane.

The mixture obtained has 16 parts of water added to it at 35 C. and, after cooling to 0 C., parts of ice and 1 part of aminosulfonic acid are added. After an hour, a solution of 20.5 parts of anhydrous sodium acetate in 100 parts of Water is added to the mixture and the precipitated dye is filtered off and dried under reduced pressure at 50 C. after it has been washed with a saturated aqueous solution of sodium acetate and Water.

The dye dyes cellulose acetate blue shades of good Waste gas and light fastness.

Example 42 12.4 parts of 2,4-dinitro-6-brom-l-aminobenzene are introduced at 0 to 5 C. into a mixture of 16 parts of nitrosylsulfuric acid with a content of 13.1% of dinitrogen trioxide and 14 parts of concentrated sulfuric acid and stirred for 12 hours. Then the solution is poured onto parts of ice and water, 1 part of aminosulfonic acid is added and the solution filtered into a coupling solution prepared analogously to Example 41 and the dye isolated as there described. It dyes cellulose acetate reddish blue shades of good fastness to light.

Example 43 8.25 parts of N-ethyl-N-(Z-hydroxyethyl)-aminobenzene, 10 parts of dioxane and 7.3 parts of 2,3-dichlorotetrahydrofurane are heated together for 15 minutes at 95 to 98 C. After cooling to room temperature, 5 parts of concentrated hydrochloric acid and 25 parts of water are added. Into this solution, a diazo solution is allowed to flow which has been prepared as described in Example 42 with the difference that 8.25 parts of 2-amino-5-nitrobenzonitrile are used instead of 2,4-dinitro-6-brom-1- aminobenzene.

The whole is worked up as in Example 41 and a dye is obtained which dyes polyethylene terephthalate ruby-red shades of excellent fastness to rubbing.

Example 44 Example 45 100 parts of a fabric of cellulose 2 /2-acetate are dyed in a bath of 15 parts of the dye from Example 33, 2 parts of Marseilles soap and 4000 parts of water for 90 minutes at 98 to 100 C.

A greenish blue dyeing is obtained with very good waste gas fastness.

Example 46 100 parts of a fabric of cellulose triacetate are dyed in a bath of 2 parts of the dye of Example 17, 4 parts of Marseilles soap and 4000 parts of Water for 60 minutes at 98 to 100 C.

A ruby-red dyeing of very good Waste gas fastness and good light fastness is obtained.

We claim: 1. An azo dye of the formula R2O l R; O

13 wherein D represents a diazo component selected from the class consisting of R represents a radical selected from the class consisting of lower alkyl, B-hydroxyethyl, B-cyanoethyl and R represents a radical selected from the class consisting of CII2CH: CH2CH and CH2CH- 1 OHzCl OH2CN 1 4 3. The dye of the formula 1 CzHs onnoJ 4. The dye of the formula 0 C H3 I /C2H5 O2NN=NF N c2n4o /O 5. The dye of the formula H 1 when l NHCOCI'Ig References Cited in the file of this patent UNITED STATES PATENTS Dickey et a1 May 7, 1940 OTHER REFERENCES Gustus Liebigs Annalen der Chemie, volume 596 35 (1955), pages 113 to 115.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 117,956 January 14, 1964 Gue'n-t-em- -Lange et a1.

It is hereby certified that error appears in the above numbered pat- (ant requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 13 to 17, for the ,f-irstuformula reading:

same column, line 67, for "trifuoromethyl" read trifluoromethyl column 8, Example 24, under the heading "Coupling. components", for that'portion of the formula reading:

H read Column 9, Example 29 under the heading "Coupling components", -For that portion of the formula reading:

C H H read C H O' c1 ell- Signed and sealed this 14th day of July 1964.

(SEAL) fittest:

Rsim G. "JOHNSON EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. AN AZO OF THE FORMULA 